Creation of Special Shape Nano-scale Materials by Using Templates Derived from Higher Ordered

通过相应的聚合物阴离子与二氧化碳反应，合成了链端羧基聚苯乙烯和核官能化三臂星形支化羧基聚苯乙烯。以芳香族或脂肪族氨基的苯基乙烯基亚砜为原料，通过活性阴离子聚合反应合成了α功能化的芳香族或脂肪族氨基的聚苯基乙烯基亚砜S(PPVs)。将上述羧基功能化的聚苯乙烯与胺官能化的PPVs通过离子键作用，合成了新型嵌段共聚物和不对称星形支化聚合物。这些聚合物被纺制成薄膜，然后在150℃下进行热处理，将其PPVs链完全转化为导电的聚乙炔(PA)链段。从而制备出各向异性导电膜。聚苯乙烯和PA链段在分子水平上进行相分离，然后进行自组织，形成纳米级的周期性有序片层和球状超结构。SAX、透射电子显微镜、扫描电子显微镜和原子力显微镜分别证实了这种结构的形成。观察到它们的大小、周期性和形状取决于PA的链长和组成。片状或球状纳米导电材料的分离现在正试图通过离子键的断裂和随后从薄膜中去除聚苯乙烯片段来进行。

Both chain-end-functionalized polystyrene with carboxyl group and core-functionalized 3-arm star-branched polystyrene with carboxyl group were synthesized by the reacting of the corresponding polymer anions with carbon dioxide. α-Functionalized poly(phenyl vinyl sulfoxide)s (PPVS) with aromatic or aliphatic amino groups were also synthesized by the living anionic polymerization of phenyl vinyl sulfoxide with the amine-functionalized initiators. New block copolymers and asymmetric star-branched polymers were prepared by the reaction of the above-mentioned carboxyl-functionalized polystyrene with amine-functionalized PPVS via ion bond formation. These polymers were spin-cast into films, followed by thermal treatment at 150℃ to completely convert their PPVS chains into conductive polyacetylene (PA) segments. Thus, anisotropic conductive films were prepared. Both polystyrene and PA segments were phase-separated at molecular level, followed by self-organization to afford nano-scale periodic ordered lamella and sphere superstructures. The formation of such structures were confirmed by SAX, TEM, SEM, and AEM, respectively. It was observed that their sizes and periodicities as well as shapes were depended upon the chain lengths of PA and compositions. The isolation of the sheet-like or sphere-like nano conductive materials is now being attempted by the cleavage of the ion bonds and subsequent removal of polystyrene segments from the films.